Process for vat dyeing cellulosic textile materials



United States PatentO 3,339,999 PROCESS FOR VAT DYEING CELLULOSIC TEXTILE MATERIALS Arnold Wick, Therwil, Switzerland, assignor to Ciba Limited, Basel, Switzerland, a Swiss company No Drawing. Filed June 17, 1963, Ser. No. 288,447 Claims priority, application Switzerland, June 19, 1962,

7,38 /62 23 Claims. (Cl. 8-34) The present invention provides new, valuable vat dyestufis that contain at least one vat-stable phosphoric acid grouping and at least fused rings or at least 2 vattable systems. 1

The term vat dyestufls includes dyestuffs that contain keto groups and, that are capable of conversion by reduction into a so-called-leuco form or vat which has better aflinity for natural and regenerated cellulose fibers than the non-reduced form, and which can be reconverted by oxidation into the original chromophoric system. As suitable vatdyestufis there may be mentioned those of the perylene tetracarboxylic acid series, the naphthalene 3,339,999 Patented Sept. 5, 1967 of these groupings are the following, in which F advantageously represents an aromatic nucleus that constitutes a component of the dyestuff molecule and that can be, for example, an external aryl radical, especially a phenyl radical FCH C-OH OH F-0;P OF

, F-O-CHa-OHp-OP-OH Also stable are groupings of a similar kind having a carbon-phosphorus bond, for example,

tetracarboxylic acid series, the pyrenequinone series, the

benzo series and the naphthoquinone series, indigoid vat dyestufls and more especially vat dyestufis of the anthraquinone series, for example,those-which contain a 9:10 dioxo-anthracene ring and-at least two fused carb'oxylic or heterocy-clic rings, or which consist of a plurality of anthraquinone units. As anthraquinone dyestufis there may be mentioned more especially those that consist of two or more anthraquinone units that are joined together either directly, or for'example, through an -'-NH bridge,

a -CH=N.--N CH-- bridge, an' alkylene or arylene diamine bridge or through a dicarboxylic acid radical, or polycarboxyli'c acid radicalor through one o'r several imidazole, triazole, triazine, cyameluric. acid, pyrimidine,

quinazoline,"oxazole, or oxdiazole or thiazole'rings.

As examples" of anthraquinone vat ,dyestufis'theref may be mentioned those "of the following 'clas'se's'z' thiophan- I or through an thraquinones, anthrapyrimidines, anthrapyridones, iso'thi azole anthrones, vquinazolineanthraquinbnes, oxazole anthraquinones, thiazole anthraquinones," oxdia' zole anthraquinones, anthraquinonyltriazoles, 'acylamino anthraquinones, pyrazole anthraquinones, dipyrazole .anthronyls,t

pyrazino anthraquinones, 'hydrazone anthraquinones, azomethine anthraquinones, aza anthraquinones; azabenzanthrone, anthraquinone acridone, indanthrones, thioxanthone anthraquinones, anthrimides, anthrimidecar bazoles, dihydro acridines, anthanthrones, pyranthrones,dibenzpyrene quinones, dibenzanthrones, isodibenzanthrones, flavanthrones, 'acedianthrones, phthaloyl compounds of binuclear and polynuclear hydrocarbons. The term vatstable phosphoric acid grouping? refers to those phosphoric acid and thiophosphori'c acid groupings that are not split off in an aqueous vat under normal dyeing conditions so that the phosphoric acid grouping is still presentin the dyes'tufl obtained by oxidationof the vat and canbe de- Phosphoric acid groupings that are not vat-stable are those that are bonded to the dyestufi molecule through an -'SO -a1kylene-O-bridge +8 O l II-I-alkylene-O-bridge In these cases, extensive attack takes place, whereby the phosphoric acid grouping is split off in the vat.

In addition .to these substituents, the vat dyestufis of the invention may also contain the usual substituents, for

tected, for example, by elementary analysis (phosphorus).

Groups that are also considered stable are those phosphoric acid groupings that can be split oil under extreme condi- 5 tions which do not obtain in ordinary vat dyeing processes,

or groups of the kind defined that contain a halogen atom l bonded to phosphorus or an O-alkyl group which is rel placed by an OH group during the vattingprocess and which is then normally present in the form of an alkali salt.

It is not only those phosphoric acid groupings in which the phosphorus is bound directly to a carbon atom which have proved to be stable. The surprising observation has been made that those groupings in which the phosphorus is bound to a carbon atom of the dyestuft molecule through an oxygen atom are likewise stable. The most important example, halogenatoms, alkyl and alkoxy groups, acylamino groups, andthe like, and also reactive groups (or atoms) which, it necessary, can enter into chemical link age with onejanot lier or with the fiber. Examples of such 1 substituents are-primarily sulfato alkyl groups, chlorotriaz'inyla'mino groups, chloropropionylamino groups and chloropyrimidine groupings. p

The new dyestuffs are obtained by methods inthemselves known, for example, by the introduction of a phosphoric acid grouping of the kind defined into vat dyestuffs that contain at least 5 fused rings or at least 2 vattable systems, or into intermediate products that are converted into vat dyestuffs of the kind defined by the introduction of such a group or that are subsequently converted into vat dyestuifs in known manner. Thus, vat dyestuffs can be phosphorized directly, for example, by means of phosphorus pen toxide or by means of polyphosphoric acids, or vat dyestuffs that contain mobile substituents in their molecule, for example, mobile halogen atoms, can be converted into the corresponding phosphorus-containing derivatives by means of metal phosphites (for example,

sodium, potassium or ammonium phosphites) or by means of phosphorus acid esters (for example, trialkyl phosphites or triaryl phosphites) by exchanging the mobile I substituents. Phosphorus-containing derivatives can-likewise be obtained by directly reacting vat dyestuffs with aluminum chloride-phosphorus trichloride mixtures, advantageously at a raised temperature and under superatmospheric pressure and then subjecting them to hydrol-' ysis and oxidation. The vat dyestuifs of the invention can likewise be prepared by directly phosphating vat dyestuffs that contain phosphatable hydroxyl, mercapto or at most secondary amino groups, for example, by means of phosphorus oxychloride, phosphorus oxybromide, othoand polyphosphoric acid, P PSBr P 8 and the phosphating agents analogous to those described in United States Patent No. 2,183,998, patented Dec. 19, 1939, to James G. McNally et al.

The introduction of phosphoric acid groups into vat dyestuffs in accordance with the invention can also be carried out simultaneously with the manufacture of the dyestulTs by using starting materials that already contain the desired grouping. Thus, valuable hydrophillic vat dyestuffs can be prepared, for example, by acylating amino-anthraquinones with acrylating agents that contain a phosphoric acid group of the kind defined. As acylating agents for use in the said process there may be mentioned, for example, phosphato acetic acid chlorides and more especially phosphato halides of the general formula 010 o-(0Hz)..-1 h

in which n represents an integer of a value not greater than 2, X represents a direct bond or an oxygen atom or an ethylsulfone group or a sulfonic acid N-ethylamide group or an alkyl group or an alkoxy group (having an oxygen atom on one side or on both sides) and Y and Z each represents a halogen atom (especially a chlorine atom) or a substituted or unsubstituted amino group or an HS group or an arylmercapto or alkylmercapto group or an aryloxy or alkyloxy group or more especially a hydroxyl group or an R-O group (R representing a cation). As such compounds there may be mentioned, for example, those of the formulae (in which Y and Z have the meanings given above) or especially chloroformylaryl or -aralkylphosphonic acid derivatives, for example, those of the formulae in which X, Y and Z have the meanings given above,

which is bound either directly or through an arylamino, aryloxy, arylthio, alkylamino or alkylarylamino bridge.

As such compounds there may be mentioned, for example, those having the following formulae om or y DyestufiFs whose phosphoric acid group or groups are bound through a heterocyclic ring, for example, through a pyrimidine ring or through a triazine ring, as, for example, in the case of the last five formulae above, can also be prepared in accordance with the invention by using as starting materials dyestuffs that already contain a heterocyclic ring that contains at least one labile halogen atom and replacing the labile halogen atoms, either wholly or in part, with the appropriate radical by reacting the dyestuffs with an amine that contains the phosphoric acid grouping. For example, a 2:4-dichloro-6- anthraquinonylaminotriazine dyestuif or a 2 chloro 4:6- bisanthraquinonylamino dyestuif can be reacted with an amine of the formula in which Q represents a direct bond or a CH group or a -CH CH O bridge.

If there is already a phosphoric acid group of the kind defined present in the amino-anthraquinones to be acylated, as in the case of the 1-amino-4-, and -8-phosphatobenzoylaminoanthraquinones for example, the ordinary kinds of acylating agent can be used for acylating the free amino group.

As examples of acylating agents there may be mentioned those with or without further groups imparting solubility in Water, for example, halides, of aliphatic or advantageously aromatic polybasic acids, for example, those of oxalic acid, sulphobenzoic acid, sulfo-acetic acid, succinic acid, glutaric acid, phthalic acid, isophthalic acid, terephthalic acid, azobenzene dicarboxylic acid, azodiphenyl dicarboxylic acid, perylene tetracarboxylic acid dianilide-dicarboxylic acid, anthanthrone dicarboxylic acid, furanand thiophene dicarboxylic acid and more especially the halides of barbituric acid and cyanuric acid or the condensation products thereof, by the use of which the valuable products of the invention can be formed directly, that contain two or more anthraquinone radicals of the last-mentioned acylating agents there may be mentioned, for example, cyameluric acid chloride and the monocondensation products thereof, cyanuric chloride and its analogous monocondensation products with alcohols, phenols, me-rcaptans, ammonia and amines, especially sulfoaryl amines with or without dyestutf character,

2 :4: 6-trichloropyrimidine,

2 :4 6-tribromopyrimidine,

214:5 6-tetrachloropyrimidine,

2:4-dichloro-G-methylpyrimidine,

2 4-dichloro-5 -nitropyrimidine,

2:4-dichloro-S-nitro-6-methylpyrimidine,

2 4: 6-trichloro-S-nitropyrimidine,

2:6-dichloropyrimidine-4-carboxylic acid chloride,

2:6-dichloropyrimidine-5-sulfonic acid chloride,

2:4-dichloropyrimidine-5-sulfonic acid,

2-(3'- or 4'-carboxyphenylamino)-4:6-dichloropyrimidine,

2-(3- or 4 carboxyphenylamino)-4:6:S-trichloropyrimidine or the compounds of the formulae O OOH N 01-5 and LNHO

The acylation with the above mentioned acylating agents that contain the dichlorotriazine ring can be carried out in such a manner that first cyanuric chloride is reacted in a molar ratio of 1:1 with an anthraquinone derivative that contains an acylatable amino group and a phosphato group, and the resulting dichlorotriazine condensation product is reacted with an identical or different amino-anthraquinone until at least some of the exchangeable halogen atoms are replaced by stable radicals.

The acylation process of the invention can be carried out in an inert organic solvent, for example, in nitrobenzene, chlorobenzene or ortho-dichlorobenzene, at a raised temperature. However, in many cases it is also possible to perform the reaction in an aqueous medium, advantageously in the presence of an agent capable of binding 6 acid, for example sodium acetate, sodium hydroxide or sodium carbonate.

Another method of carrying out the present manu facturing process consists in converting the character- 5 istic phosphoric acid grouping into vat dyestuffs, for example, by carbazolation or the formation of oxdiazole or acridone after the said grouping has been introduced.

The dyestuffs obtained by the process of the present invention are new. They are suitable for dyeing a very Wide variety of materials, and especially for dyeing or printing textile materials of natural or regenerated cellulose by the usual vat dyeing or printing methods. The dyeings and prints so obtained are generally fast to chlorine and are distinguished by their excellent fastness to light and excellent properties of wet fastness. In particular, their fastness to soda boiling is good.

The dyeings produced with the dyestuffs of the invention are also fast to dry cleaning and migration. The dyed fabrics can therefore be coated with synthetic resins, for example, polyvinyl chloride, without the dyestufl migrating into the resin, which is particularly important in the manufacture of artificial leather.

As compared with the conventional vat dyestuffs, the vat dyestuffs of the invention, which contain at least one OH group or SH group bound to the phosphorus atom or a radical easily convertible into such a group, possess a better levelling and penetrating power. When used for dyeing in circulating liquor machines the water-soluble vat dyestuffs in particular do not give rise to faulty dyeings caused by the precipitation of reoxidized dyestufi when foam is formed, and the pigmenting operation that is necessary in dyeing wound packages, for example, cheeses, or in dyeing tricots on a winch machine, with the conventional vat dyestuffs is superfluous with the dyestuffs of the invention. Moreover, they can be used in the form of solutions in fast-running pad-dyeing processes and do not have to be in the form of finely dispersed commercial preparations or in the form of special pastes, so that the disadvantages associated with such forms (instability of the paste, dusting and the need for one or more operations to prepare finely dispersed powders) do not arise. Finally, they can generally be vatted very easily, often at room temperature and, if desired, with mild reducing agents, which yield unsatisfactory results when used for conventional vat dyestuffs.

The process of vatting in a stock vat, which is a safety measure still in general use, can be omitted, and the dyestntf can be vatted in the dyebath at the commencement of the dyeing operation.

By virtue of the fact that the dyestuffs are easily dissolved and are converted into the leuco form with great rapidity, they can be used with advantage in high-speed dyeing and printing processes which do not allow of a long vatting time. When a suitable reducing agent is used which is virtually inactive at room temperature but which has a reducing action at a raised temperature, for example, in a steaming operation, the dyestulfs of the invention can also be applied, for example by a one-bath impregnating/steaming process.

Compared with the vat dyestuffs known hitherto, which contain non-eliminable sulfuric acid groups, the dyestuffs of the invention have the advantage that there is virtually no danger of fiber damage being caused by free phosphoric acid groupings adhering to the dyestnfi, even if acidification after dyeing has not been carried out properly.

The dyestuff of the invention exhibits a very good solubility in the vat and, in most cases, require a substantially smaller amount of reducing agent than is generally needed when dyeing with conventional vat dyestuffs, especially when dyeing in circulating liquor machines.

The following examples illustrate the invention. Unless otherwise stated, the .parts and percentages are by weight, and the relationship of parts by weight to parts by volume 75 is the same as that of the gram to the milliliter.

2 parts of the vat dyestuff intermediate product of the formula NHCO COHIII h) are dissolved at the boil in 100 parts of dry nitrobenzene, and the solution so obtained is cooled to 140 C. while stirring. At this temperature, 2.2 parts of para-chloroformylphenyl dichlorophosphate in 20 parts of nitrobenzene are added and the whole is stirred for hours at 140 to 145 C. The dyestutf that precipitates thereby is isolated by filtration at 90 C., washed with a small amount of nitrobenzene and with warm dry benzene and then dried in vacuo at 60 C. The product so obtained has a phosphorus content of 5.69% and dyes cotton and regenerated cellulose strong yellow tints possessing good properties of fastness when applied from an alkaline hydrosulfite vat.

Dyeing prescription 1 part of the dyestuff so obtained is vatted at 45 C. in 100 parts of water with 2 parts of sodium hydrosulfite and in the presence of 4 parts by volume of sodium hydroxide solution of 30% strength. The stock vat so obtained is added to a solution of 4 parts by volume of sodium hydroxide solution of 30% strength and 2 parts of sodium hydrosulfite in 2000 parts of water. 100 parts of cotton are dyed for 1 hour at 40 to 50 C. in the dyebath so obtained in the presence of parts of sodium chloride. The cotton is then squeezed, oxidized in the air, rinsed, acidified, rinsed again and then soaped at the boil.

EXAMPLE 2 2 parts of the dyestufr obtained in the manner described in Example 1 are vatted at 40 to 45 C. and reoxidized with air. The dyestuif is then precipitated from the resulting yellow-brown solution by the addition of 100 grams of sodium chloride per liter. The sodium salt of the product changed by hydrolysis is filtered ofll, washed with a sodium chloride solution of 5% strength until the washings run neutral, and then dried.

The new water-soluble dyestutf corresponds, in the form of the free acid, to the formula HNC CONH o I II II HO;PO CONH o 0 and dyes cotton and regenerated cellulose from an alkaline hydrosulfite vat, yellow tints similar to those obtained by the product described in Example 1 that exhibit the same properties of fastness.

When applied by the process described in Example 18 of Swiss Patent No. 365,698 patented Nov. 30, 1962, to Ciba Aktiengesellschaft, Basel, Switzerland, the above dyestutf yields a yellow print possessing good properties of fastness.

Dyeing prescription 2 parts of dyestuif are dissolved or suspended in 500 parts of water at 60 C. The dissolved or suspended dyestutf is vatted in a dyebath that contains 20 parts of sodium hydroxide solution of 30% strength and 12 parts of sodium hydrosulfite in 3500 parts of Water. 100 parts of well-wetted cotton are entered into th dyebath so prepared at 60 C. and dyed therein for 10 minutes at that temperature in the presence of 60 parts of sodium chloride. The temperature is then raised to 70 C. and a further 60 parts of sodium chloride are added. After 15 minutes, the dyeing temperature is raised to C., and dyeing is continued at that temperature for 15 minutes. The cotton is then removed from the dyebath, oxidized, neutralized, thoroughly soaped at the boil, rinsed, first in warm Water and then in cold water, and then dried.

EXAMPLE 3 2 parts of the intermediate product mentioned in Example 1 are condensed with 2.2 parts of meta-chloroformylphenyl dichlorophosphate in the manner described in Example 1, and the resulting product is vatted in a manner analogous to that described in Example 2.

The water-soluble dyestuif so obtained, which, compared with the product described in Example 2, is metaisomeric in respect of the position of the phosphato group, dyes cotton and regenerated cellulose yellow tints possessing good properties of fastness when applied from an alkaline hydrosulfite vat according to the dyeing prescription given in Example 2.

EXAMPLE 4 2.5 parts of the finely-ground dyestufi intermediate product of the formula 0 O NH: H u N II u 0 O NH:

are stirred for 12 hours at 140 C. in parts of dry nitrobenzene with 1.65 parts of para-chloroformylphenyldichlorophosphate. The condensation product is isolated in the manner described in Example 1 and revatted in the manner described in Example 2.

The dyestutf thus formed, which is readily soluble in water, corresponds, in the form 1 and dyes cotton and regenerated cellulose strong, fast blue and dyes cotton and regenerated cellulose strong, olivetints When applied from an alkaline hydrosulfite vat ac green tints possessing excellent properties of fastness when cording to the dyeing prescription given in Example 2. applied from an alkaline hydrosulfite vat according to the EXAMPLE 5 dyeing prescription given in Example 2.

5 A similar dyestulf is obtained -'n the above manner when 2.3 parts of finely ground 5:5'-d1arnin0-1:1'-d1anthriusing para chloroformylphenyl dichlorophosphate as mide carbazole are stirred for 24 hours at 120 to 130 C. acylating agent.

in 100 parts of dry nitrobenzene with 3.3 parts of meta- When applied by the pad-jig process described in Exchloroformylphenyl-dichlorophOsphate, and working p am'ple 6 of Swiss Patent No. 365,698, patented Nov. 30,

is carried out in the manner described in Example 4. The 1962, to Ciba Aktiengesellschaft, Basel, Switzerland, the

water-soluble dyestufi that is formed thereby corresponds, 10 above dyestuffs yield olive dyeings possessing excellent in the form of the free acid, to the formula properties of fastness.

H I N H I u HO-PO 0 I g H0 P OH O-OONH o HNQO- 0H and dyes cotton and regenerated cellulose strong, fast EXAMPLE 7 brown-yellow tints when applied from an alkaline hydrosulfite vat according to the dyeing prescription given in 3.75 parts of 2-amino-7-cl1loro-3:4-phthaloylacridone Example 2. are stirred for 24 hours at 130 to 140 C. in 50 parts of When using para-chloroformylphenyl-dichlorophosdry nitrobenzene with 3.3 parts of para-chloroforrnylphate as acylating component there is obtained in the phenyl-dichlorophosphate, and working up is carried out above manner a dyestufi that is isomeric in respect of. the in the manner described in Example 4. There is obtained position of the phosphate group and that yields simila a water-soluble blue vat dyestuff whose free acid cortints having the same degree of fastness. responds to'the formula EXAMPLE 6 2.3 parts of the finely-ground dyestufi' intermediate product of the formula r 1 i .j OH 40 I1 I o i u N o on rv-ooGor-orr I EXAMPLE 8 3.3 parts of the thioindigoid dyestuff intermediate prod- V uctof the formula l) r are stirred for 24 hours at 120 to 130 c. in 100 parts or g dry nitrobenzene with 1.65 parts of meta-chloroformylphenyl-dichlorophosphate, and further processing'is carried out in the manner described in Example 4. The dyestuff thus formed, which is readily soluble in water, corresponds, in the form of the free acid, to the formula Q are stirred'for 24 hours at 120 to 130 C.'in 50 parts of dry nitrobenzene with 3.3 parts of para-chloroformyl- 0H phenyl-dichlorophosphate. After working up in the NBC 0 manner described in Example 4 there is obtained a salmon- 0 pink water-soluble vat dyestufi whose free acid corre- H sponds to the formula 1 O 0 4 0 H s NHC 0G0 ZOEI II o H stirring. After 16 hours, the temperature is raised to 180 EXAMPLE 9 to 185 C. The reaction mixture is maintained at that 2.1 parts of finely-ground aminoacedianthrone are temperature for 5 hours, after which stirring is continued stirred for 24 hOLIIS at 120 t 130 C. 111 100 parts Of dry for 1 hour at 200 to.2() c whereupon working up is nitrobenzene with 1.65 parts of meta-chloroformylphenyl- 5 carried o t i the m nn r described in Example 4. The

dichlorophospha-te, and working up is carried out in the water-soluble dyestufi thus obtained corresponds, in the manner described in Example 4. The water-soluble dyeform of the free acid, to the formula OH OH 0 0 stuff that is formed thereby corresponds, in the form of and dyes cotton and regenerated cellulose strong red tints the free acid, to the formula possessing very good properties of fastness when applied according to the dyeing prescription given in Example 2. H A similar dyestuff is obtained in the above manner when using meta-chloroformylphenyl-dichlorophosphate. NH-CO Cg EXAMPLE 12 2.7 parts of the finely-ground vat dyestulf intermediate product of the formula o NH, H2N h) o 2. W L

II I! (ll) 0 NH: HaN O and dyes cotton and regenerated cellulose brown tints F to in the iiourse of 1 possessing an excellent fastness to light when applied ac- Whfle Surfing 150 Parts of dry nltrobenzenei the cording to the dyeing prescription given in Example 2. presence of 4.1 parts of parachloroformylphenyl-dichloro- A similar dyestuif is obtained in the above manner when 'phosPhate f f dlmethylformamlde, and the using para-chloroformylphenyl-dichlorophosphate, I'eact1on m xture is malnta ned at that temperature for 20 hours. Stirring 1s then continued for a further hour at 160 EXAMPLE to 165 C., and working up is then carried out in the 2.4 parts of finely-ground aminodibenzanthrone are remanner described in Example 4. acted with 1.65 parts of meta-chloroformylphenyl-dichlo- The dyestufi thus formed, which is readily soluble in rophosphate in the manner described in Example 9, and I water, corresponds, in the form of the free acid, to the working up is carried out in the manner described in Ex- 40 formula 0 NH] HgN 0 II 0 H m y N Ll .1 A 110:1 0G0 0NH NHO0OP:0H HO OH ample 9. The Water-soluble dyestulf that is formed thereand dyes cotton and regenerated cellulose strong, blue by corresponds, in the form of the free acid, to the formula tints when applied according to the dyeing prescription NH-CO 0 PZOH (I) (in and dyes cotton and regenerated cellulose blue-green tints given in Example 2. A similar dyestulf is obtained in the possessing a high fastness to light when applied according above manner when using meta-chloroformylphenyl-dito the dyeing prescription given in Example 2. chlorophosphate.

A similar product is obtained when using para-chloroformylphenyl-dichlorophosphate as acylating agent. EXAMPLE 13 EXAMPLE 11 2.2 parts of l-aminoanthraquinone and 1.8 parts of 2.9 parts of the finely-ground vat dyestutf intermediate 3:5-dichloroformylphenyl-dichlorophosphate are heated product of the formula to C. in the course of 20 minutes, while stirring, in

are suspended in 200 parts of dry nitrobenzene. 4.1 parts 50 parts of dry nitrobenzene, and the mixture is stirred 0f parachloroformylphenyl-dichlorophosphate and 0.2 for a further 15 minutes at that temperature. The yellow, part of dimethylformamide are added and the whole is crystalline condensation product that is formed is isolated heated to to C. in the course of 6 hours, while 75 by suction filtration after cooling the reaction mixture,

13 Washed with benzene, and then dried in vacuo at 60 C. It has a phosphorus content of 4.9%.

2 parts of the above product are revatted in the manner described in Example 2. The dyestuff that is formed thereby, which is readily soluble in the vat, corresponds, in the form of the free acid, to the formula O O-HN ll H o and dyes cotton and regenerated cellulose yellow tints possessing good properties of fastness when applied according to the dyeing prescription given in Example 2.

EXAMPLES 14 TQ 20 Further valuable dyestuffs of the kind defined are obtained from 3:5 dichloroforrnylphenyl-dichlorophosphate in the above manner when using substituted aminoanthraquinone derivatives such as v Exlarrnple Amino-anthraquinone Tint 14 l-amino-4benzoylamino-anthraquinone Red.

15 l-amino-dbenzoylamino-anthraquinone Yellow.

16 l-aminol-phenylmercapto-anthraqui- Red.

none.

17 1-amino-5-phenylmercapto'anthraqui- Golden-yellow.

none.

18 1-aminoA-anilido-anthraquinone Reddish-blue.

19 l-arm'no4-methoxy-anthraquinone Golden-orange;

20 l-amino-S-chloranthraquinone Yellow.

EXAMPLE 21 2 parts of the non-revatted dyestuff of Example 17 are introduced at 15 to 18 C. into 20 parts by a volume of sulfuric acid of 98% strength and stirred therein for 45 minutes at room temperature. The mixture is then discharged on the 200 parts of ice, filtered, and the filter residue is washed with a sodium chloride solution of 1% strength until the washings run neutral and then dried in vacuo at 60 C.

The sulfonated product of 8.9% in addition to a phosphorus content of 3.1% and, after being revatted in the manner described in Exam.- ple 2, yields a dyestufr that is readily soluble in water and that dyes cotton and regenerated cellulose fast goldenyellow tints when applied according to the dyeing prescription given -in Example 2. 1

The dyestuff in Example 16 can also be converted in an analogous manner into a product that contains sulfo groups.

EXAMPLE 22 i 4.5 parts of 4-B-acetoxy-ethoxybenzoic acid (prepared by acetylating 4-B-hydroxyethoxybenzoic acid with acetic anhydride), 2.6 parts of thionylchloride and 0.2 part of dimethylformamide are converted into an acid chloride solution by stirring for 18 hours at 85 C. in 50 parts of dry nitrobenzene. 4.2 parts of finely-ground aminoacediso obtained has a sulfur content anthrone in 100 milliliters of dry nitrobenzene are added, and the temperature is raised to 140 to 145 C. in the course of 3 hours. After 22 hours, the temperature is raised to 160 to 165 C. and stirring is continued for a further 6 hours. The reaction mixture is then allowed to cool. It is then filtered and the filter residue is washed with a small amount of nitrobenzene and alcohol and then dried in vacuo at 60 C.

5.9 parts of the dried and finely-sieved product are introduced at 5 to 10 C. into parts by volume of sulfuric acid of strength and the whole is stirred for 3 hours. The brown, viscous paste that is formed is discharge onto the 800 parts of ice and water, filtered ofi, washed with water, finely dispersed by suspending it in 1000 parts of water while stirring rapidly, suction filtered, washed until the washings run neutral and then dried in vacuo at 60 C. The dyestufi intermediate product of the formula NHOOOOCHiGHEOH is thus obtained.

2.5 parts of the said dyestuif intermediate product are finely sieved, introduced into 60 parts of polyphosphoric acid at C. and the whole is stirred at that temperature for 2 hours. The resulting dark brown paste is discharged into 600 parts of water, stirred for 1 hour, filtered off, washed with warm water until neutral and then dried in vacuo at 100 C. After being revatted in a manner analogous to that described in Example 2, the product so obtained has a phosphorus content of 4.0%.

The dyestuif so obtained, which is readily soluble in the vat, corresponds, in the form of the free acid, to the formula NHC OC OCHzCHgO EOH ll and dyes cotton and regenerated cellulose fast brown tints when applied according to the dyeing prescription given in Example 2.

EXAMPLE 23 4.6 parts of the finely-ground intermediate product described in Example 6 and an acid chloride solution prepared from 3.4 parts of 4-fi-acetoxyethoxybenzoic acid, 1.9 parts of thionyl chloride and 0.2 part of dimethylformamide in 50 parts of dry nitrobenzene in the manner described in Example 22 are stirred for 24 hours at to C. and subsequently for 6 hours at to C. in 100 parts of dry nitrobenzene, and the resulting product is Worked up in the appropriate manner.

4.5 parts of the condensation product so obtained are HO;P oomomo-O-o OHN scribed in Example 22 is readily soluble in the vat, corresponds, in the form of the free acid, to the formula NHOO-OOCHQCHiOP-OH o and dyes cotton and regenerated cellulose olive-green tints possessing excellent properties of fastness when applied according to the dyeing prescription given in Example 2.

EXAMPLE 24 6.7 parts of 4-B-acetoxyethoxybenzoic acid, 3.9 parts of thionyl chloride and 0.2 part of dimethylformamide are converted into an acid chloride solution in parts of dry nitrobenzene in the manner described in Example 22, the 65 l O o l I HO;POCH2CH2OOC OHN NH0 2.5 parts of the hydroxy-ethoxy intermediate product so obtained are stirred for 6 hours in parts of polyphosphoric acid at 55 to C., and working up is then carried out in the manner described in Example 22. A product with a phosphorus content of 5.8% is obtained.

The dyestuif so obtained, which is readily soluble in the vat, corresponds, in the form of the free acid, to the formula i O N O I II 0 II ll O O NHCO OCH2OHzOP OH OH and dyes cotton and regenerated cellulose strong orange tints possessing very good properties of fastness when applied according to the dyeing prescription given in EX- ample 2.

EXAMPLE 25 2.7 parts of the finely ground dyestuif intermediate product described in Example 12 are added at C. to an acid chloride solution prepared from 4.5 parts of 4-fiacetoxy-ethoxybenzoic acid in a manner described in Example 22. The temperature is then raised to to C. in the course of 3 hours and stirring is continued at that temperature for 4 to 5 hours. After the addition of 500 parts of benzene, the reaction mixture is cooled while stirring, filtered, the filter residue is washed with benzene and then dried in vacuo at 60 C.

4 parts of the condensation product so obtained are hydrolyzed in 60 parts by volume of sulfuric acid of 85% strength in the manner described in Example 22 to form the corresponding hydroxyethoxy intermediate product.

The dyestuff obtained by phosphating 2 parts of the intermediate product so obtained at 55 to 60 C. in 50 parts of polyphosphoric acid and further treatment in the manner described in Example 22 is readily soluble in the vat and corresponds, in the form of the free acid, to the formula It dyes cotton and regenerated cellulose blue tints possessing excellent properties of fastness when applied according to the dyeing prescription given in Example 2.

EXAMPLE 26 3.9 parts of para-carboxybenzylacetate (cf. J. Amer. Chem. Soc., vol. 72, 5152 [1950]) are converted into an acid chloride solution with 1.6 parts of thionyl chloride and 0.2 part of dimethylformamide by stirring for 15 hours at 85 C. and 50 parts of dry nitrobenzene. After 7 the addition of 4.2 parts of finely-ground amino-acedi- 17 18 anthrone in 100 parts of dry nitrobenzene, processing is Example 22 is readily soluble in the vat and, in the form continued in the manner described in Example 22. of the free acid, corresponds to the formula There is first obtained the methylol intermediate prodo uct of the formula H NHOO- OH2OP OH if OH NHO O-O-OHzOH 1 0 i It dyes cotton and regenerated cellulose strong brown tints possessing good properties of fastness when applied according to the dyeing prescription given in Example 2.

EXAMPLES 27 TO 29 When Working according to the methods described in which corresponds to the hydroxyethoxy derivative de- Examples 23, 24 and 25 but using equivalent amounts of scribed in Example 22. The dyestuif obtained by phos- 25 para-carboxybenzylacetate instead of 4-[3-ocetoxyethoxyphating the said intermediate product with polyphosphoric benzoic acid, the following dye'stuflfs of the same kind are acid and further treatment in the manner described in obtained:

Example N0. Tint 0 21- NHOO CHzOP OH Olive-green. O OH N 0 (Analogous to Example 23) i N 0 ll p 28 Orange.

0 0 1 II II HO-POOH2 OONH O O NHCO OH2OP OH H 0 OH (Analogous to Example 24) 9 NH: OzN C) O 29- l Blue.

o l) I o O HO-1 OCH2 0 ONE NH0 0 'CH2OP OH H O OH (Analogous to Example 25) 19 20 EXAMPLE EXAMPLE 35 1.6 parts of :0 di para carboxyphenylphosphorlc acid are converted into an acid chloride solution with 1.8 2.4 parts of the acid potassium salt of paracarboxyparts of thionylchloride and 0.1 part of dimethylformphenyl phosphonic acid (of. A. Michaelis and Cl. Panek, amide by stirring for 16 hours at 85 C. in 50 parts of 5 Berichte, page 14, 405 [1881]), 4.3 parts of thionyl chlodry ortho-dichlorobenzene. 3.1 parts of l-amino-S-benzoride and 0.2 part of dimethylformamide are stirred for ylaminoanthraquinone are then added and processing is 12 hours at 85 C. in parts of dry nitrobenzene. The continued in the manner described in Example 45. resulting solution of the acid chloride is added at 140 The condensation product so obtained has a phosto 145 C. to 3 parts of the dyestuff intermediate product phorus content of 3.2%. The dyestutf obtained therefrom 10 described in Example 1 that has been finely divided in 100 by revatting is readily soluble in the vat and, in the form parts of dry nitrobenzene by dissolving and cooling. The

of the free acid, corresponds to the formula mixture is then stirred for 8 hours at 140 to 145 C.

O0 0111 (i ii NBC 06 It dyes cotton and regenerated cellulose fast yellow tints when applied according to the dyeing prescription given in Example 2.

After working up in the appropriate manner, the product so obtained has a phosphorus content of 5.2%.

The water-soluble dyestuff obtained therefrom by re- EXAM'PLES 31 TO 34 vatting in the manner described in Example 2 corresponds,

Further valuable dyestuffs of the kind defined are obin the form of the free acid to the formula p gut-o0 C0-HI? (I) 0 0 I! I I H 1 110-1; (JO-BIN 0 o NH-CQQr -OH HO 6H tainable in the above manner by using other substituted and dyes cotton and regenerated cellulose strong, fast ammoanthraquinones such as yellow tints when applied according to the dyeing prescription given in Example 2. Example i am r m Tim; A similar dyestuff is obtainable by the above process No. by the use of the isomeric mixture of carboxyphenylphosphonic acids. 31 l-amino--benzoylamlnoanthraquinone Red. 32 1-arnino-4-phenylmercaptoenthraqui- Red. EXAMPLE 36 HOBB- 33 l-amino-5-phcnylmercaptoanthraqui- Golden yellow.

110118. 34 l-amino-i-anilidoamhmquinone Blue- 2.3 grams of finely-ground 5 :5'-diamino-l:1'-di-anthrimide carbazole in parts of dry nitrobenzene are added The 0:Q'-di-para-carboxyphenylphosphorie acid used to an acid chloride solution of para-car-boxyphenylphosin the examples can "be prepared in the manner described 60 phonic acid prepared in the manner described in Examin British patent specification No. 912,287 of Imperial ple 35. The whole is stirred for 24 hours at to C. Chemical Industries, Ltd., published Dec. 5, 1962, by and then worked up in the manner described in Example hydrolyzing its trimethyl ester with 5 N hydrochloric 4. The water-soluble dyestuff so obtained corresponds, in acid. the form of the free acid, to the formula i HO-P-O-G O-HN ii 1 111-00 4 -011 r 21 22 and dyes cotton and regenerated cellulose strong orangethe manner described in Example 4 corresponds, in the brown tints possessing good properties of vfastness when form of the free acid, to the formula applied according to the dyeing prescription given in Example 2. II

A similar dyestuff is obtained by using the isomeric 5 0 mixture of the carboxyphenyl phosphonic acids. Z

OH EXAMPLE 37 f 4.6 parts of finely-ground 4:4'-diamino-1:l'-di-anthrimide in 150 parts of dry nitrobenzene are added to an acid chloride solution prepared from 48 parts of the acid potassium salt of para-carboxyphenyl phosphonic acid,

8.6 parts of thionyl chloride and 0.3 parts of dimethylformamide in 50 parts of dry nitrobenzene in the manner described in Example 35. The whole is then heated to l,

120 to 130 C. in the course of 5 hours, while stirring,

maintained at that temperature for hours and then and y cotton and regenerated Feuulose bmWI} tmts Working up is carried out in the manner described in 2 possessing an excellent fastness to light when applied ac- Example cordlng to the dyeing prescription given in Example 2.

4.5 parts of the product so obtained are introduced slmllar dyestufi 1S obtamed by usFlg isomeric slowly, while stirring, at C. into 100 parts by volume mixture of the carboxyphenyl Phosphomc acldsof sulfuric acid of 96% strength, and stirring is continued for 2 hours at 30 C. The black solution so obtained is 25 EXAMPLE 39 poured, while stirring thoroughly, into 1000 parts of 2.4 parts of finely-ground aminodibenzanthrone are rewater (containing 0.25 part of sodium chlorate) in the acted in a manner analogous to that described in the form of a fine jet and the whole is heated to 80 C.- preceding example with the acid chloride solution prein the course of 1 hour. After dilution with 300 parts of pared from 1.7 parts of the acid potassium salt of paracold water, the liquid is filtered at C., the filter residue 30 carboxyphenyl phosphonic acid in 180 parts of dry nitrois washed thoroughly with warm water and then dried benzene. The water-soluble dyestufi obtained by working in vacuo at 80 C. up in the same manner corresponds, in the form of the The water-soluble dyestug obtained by revat-ting in the free acid, to the formula manner described in Example 2 corresponds, in the form and dyes cotton and regenerated cellulose strong, bluish of the free acid, to the formula grey tints possessing a high degree of light fastness when (H) NH (H) o o y 0 o HO-P CO-HN NH-OO 1OH Ho OH and dyes cotton and regenerated cellulose olive-grey tints applied according to the dyeing prescription given in when applied according to the dyeing prescription given Example 2. in Example 2. This dyestuff yields fast, blue-greytints on wool when A similar dyestuflf is obtained by using 4:4-di-arninoapplied from a vat by the usual special process. 1:1'-dianthrirnidecarbazole as starting material and Work- A similar dyestuff is obtained by using the isomeric ing according to the process described in Example 36. mixture of the carboxyphenyl phosphonic acids.

Similar dyestuffs are also obtained by using the isomeric mixture of the carboxy phenylphosphonic acid.

EXAMPLE 38 EXAMPLE 40 1.7 parts of the acid potassium salt of para-carboxyphenylphosphonic acid are converted into the acid chloride solution with 3 parts of thionyl chloride in 20 parts 2.3 parts of the dyestuif intermediate product described in Example 6 are reacted according to the method deof dry nitrobenzene in the manner described in Example scribed in Example 38 with the acid chloride solution 35. 2.1 parts of finely ground amino-acedianthrone in prepared from 1.7 parts of the acid potassium salt of paraparts of dry nitrobenzene are added and the whole is car-boxyphenylphosphonic acid in the manner described in stirred for 24 hours at to C. Example 38, and then working up is carried out in a man- The water-soluble dyestulf' obtained by Working up in 75 ner analogous to that described in Example 38. The dyestuff so obtained is readily soluble in water and, in the form of the free acid, corresponds to the formula It dyes cotton and regenerated cellulose strong, olivegreen tints possessing very good properties of fastness C OHN EXAMPLE 41 2.7 parts of the finely-ground dyestuif intermediate product described in Example 12 in 100 parts of dry nitrobenzene are added to 3.3 parts of the acid chloride solution prepared from 3.3 parts of the acid potassium salt of para-carboxyphenyl phosphonic acid and 6 parts of thionyl chloride and 0.3 part of dimethylformamide in 50 parts of dry nitrobenzene in the manner described in Example 35. The Whole is heated to 140 to 145 C. in the course of 2 hours, while stirring, and is maintained at that temperature for 22 hours. Stirring is then continued for a further 2 hours at 160 to 165 C., and working up is then carried out in the manner described in Example 4. The water-soluble dyestutf so obtained corresponds, in the form of the free acid, to the formula NHCO and dyes cotton and regenerated cellulose strong, blue tints possessing good properties of fastness when applied according to the dyeing prescription given in Example 2.

A similar dyestutf is obtained by using the isomeric mixture of the carboxyphenyl phosphonic acids.

EXAMPLE 42 2.4 parts of para-carboxybenzyl phosphonic acid are converted into an acid chloride solution with 4.3 parts of thionyl chloride and 0.2 part of dimethylformamide in 20 parts of dry nitrobenzene in the manner described in Example 35, and the acid chloride solution so obtained is reacted with 3 parts of the dyestuff intermediate product described in Example 1 in the manner described in Example 35. The condensation product so obtained has a phosphorus content of 5.72%. The water-soluble dyestuff obtained therefrom by revatting in the manner described in Example 4 corresponds, in the form of the free acid, to the formula I ll NHC oQorng-on EXAMPLE 43 An acid chloride solution of para-carboxybenzyl phosphonic acid as described in Example 42 is reacted with 2.3 parts of finely-ground 5:5'-diamino-1:1'-dianthrimide carbazole in the manner described in Example 36. The water-soluble dyestufl obtained by working up the reaction product in a manner analogous to that described in Ex- 25 ample 4 corresponds, in the form of the free acid, to the formula and dyes cotton and regenerated cellulose orange-brown tints possessing very good properties of fastness when ap- 26 The dyestulf obtained therefrom by revatting according to the method described in Example 2 is readily soluble in the vat and, in the form of the free acid, corresponds to the formula plied according to the dyeing prescription given in Example 2.

EXAMPLE 44 NH0 0, oHiP 0H and dyes cotton and regenerated cellulose brown tints possessing good properties of fastness when applied according to the dyeing prescription given in Example 2.

EXAMPLE '45 1.5 parts of secondary 4:4-dicarboxydiphenylphoshonic acid are converted into an acid chloride solution with 1.9 parts of thionyl chloride and 0.1 part of dimethylformamide by stirring for 16 hours at 85 C. in 50 parts of \dry ortho-dic'hlorobenzene. 3.4 parts of l-arnino-S- benzoylamino-anthraquinone are then added, the temperature is raised to 140 C. and stirring is continued for a further minutes. After cooling the reaction mixture, washing is carried out successively with a small amount of ortho-dichlorobenzene and benzene and the material is then dried in vacuo at 60 C. The resulting condensation product has a phosphorus content of 2.8%.

It dyes cotton and regenerated cellulose yellow tints possessing excellent properties of fastness and in particular a very good fastness to light when applied according to the dyeing prescription given in Example 2.

EXAMPLES 46 TO 49 Further valuable dyestuffs of the kind defined are obtained in the above manner by using other substittued amino-anthraquinones such as Exglrnple Amino-anthraquinone Tint 46 1-amino-4-benzoylamino-anthraquinone Red.

47 l-amino-4-phenylmercapto-anthraqui- Red.

none.

48 1-amino-5-phenylmercapto-anthraqui- Golden-yellow.

no e.

49 l-amino-tanilidoanthraquinone Blue.

EXAMPLE 50 2 parts of the sieved dyestuif described in Example 48 are sulfonated in 20 parts by volume of sulfuric acid of 98% strength in the manner described in Example 21 and then worked up in the appropriate manner.

The product so obtained, which contains sulfo groups, has a sulfur content of 8.2% and, after being revatted in the manner described in Example 2, yields a water-soluble dyestuff which dyes cotton and regenerated cellulose fast, golden-yellow tints when applied according to the dyeing prescription given in Example 2.

EXAMPLE 51 5.4 parts of the finely-ground dyestutf intermediate product described in Example 12 are suspended in 125 parts of dry nitrobenzene, and 4.8 parts of phosphonic acetic acid trichloride in 20 parts of dry nitrobenzene are added to the suspension so obtained at 70 C. The temperature is then raised to C. in the course of 3 hours, while stirring, and the reaction mixture is maintained at that temperature. After 4 hours, 1 part of the acid chloride in 10 parts of dry nitrobenzene is added, stirring is continued for a further 2 hours at 100 C., and then Working up is carried out in the manner described in Example 4.

The dyestufi so obtained is readily soluble in water and, in the form of the free acid, corresponds to the formula HO OH It dyes cotton and regenerated cellulose strong blue tints possessing good properties of fastness and in particular a very good fastness to chlorine when applied according to the dyeing prescription given in Example 2.

What is claimed is:

1. In a process for the vat dyeing of cellulosic textile material the improvement which comprises employing as the vat dyestufl a vat dyestutf containing two members of: the group consisting of the anthrone, acridone and anthraquinone grouping which may be condensed to a ring system, and an acylamino group containing a phosphoric acid grouping bound to its acyl radical at least two vattable systems and at least one vat-stable phosphoric acid grouping.

2. In a process for the vat dyeing of cellulosic textile material the improvement which comprises employing as the vat dyestuif a vat dyestufl containing a vattable system consisting of at least five pured rings and containing at least one vat-stable phosphoric acid grouping.

3. In a process for the vat dyeing of cellulosic textile material the improvement which comprises employing as the vat dyestuff a vat dyestuif of the type containing two amino ant-hraquinone nuclei interconnected by the radical of a dicarboxylic acid wherein the vat dyestuff molecule contains at least one vat-stable phosphoric acid grouping.

4. In a process for the vat dyeing of cellulosic textile material the improvement which comprises employing as the vat dyestulf a vat dyestulf of the type containing two amino anthraquinone nuclei interconnected by the radical of a dicarboxylic acid the said dicarboxylic acid radical containing a vat-stable phosphoric acid grouping.

5. In a process for the vat dyeing of cellulosic textile material the improvement which comprises employing as the vat dyestuif a vat dyestulf of the type containing two amino anthraquinone nuclei interconnected by the radical of a dicarboxylic acid and further-more containing at least one additional acylamino group in the dyestuff molecule wherein at least one such acylamino group ca'rries a vat-stable phosphoric acid grouping.

6. In a process for the vat dyeing of cellulosic textile material the improvement which comprises employing as the vat dyestutf a vat dyestutf of the type consisting of two anthraquinone radicals interconnected by a heterocyclic ring and furthermore containing at least one acylamino group in the dyest-utf molecule wherein at least one such acylamino group carries a vat-stable phosphoric acid grouping.

7. In a process for the vat dyeing of cellulosic textile material the improvement which comprises employing as the vat dyestuif a vat dyestuif of the dianthrimide cabazol type which carries at least one acylamino group containing a vat-stable phosphoric acid grouping.

8. In a process for the vat dyeing of cellulosic textile material the improvement which comprises employing as the vat dyestuff a vat dyestutf containing the vattable system I; and attached thereto at least one acylamino group containing a vat-stable phosphoric acid grouping.

9. In a process for the vat dyeing of cellulosic textile material the improvement which comprises employing as the vat dyestuff a vat dyestuff according to claim 1 containing as vat-stable phosphoric acid grouping an acylamino group of the formula 10. In a process for the vat dyeing of cellulosic textile material the improvement which comprises employing as the vat dyestutf a vat dyestutf according to claim 1 containing as vat-stable phosphoric acid grouping an acylamino group of the formula 11. In a process for the vat dyeing of cellulosic textile material the improvement which comprises employing as the vat dyestuff a vat dyestuff according to claim 1 containing as vat-stable phosphoric acid grouping an acylamino group of the formula 12. In a process for the vat dyeing of cellulosic textile material the improvement which comprises employing as the vat dyestulf a vat dyestutf according to claim 4 containing a dicarboxylic acid radical of the formula 13. In a process for the vat dyeing of cellulosic textile material the improvement which comprises employing as the vat dyestuff a vat dyestutf according to claim 4 containing a dicarboxylic acid radical of the formula '14. In a process for the vat dyeing of cellulosic textile material the improvement which comprises employing as the vat dyestuff a vat dyestuff according to claim 4 containing a dicarboxylic acid radical of the formula 16. In a process for the vat dyeing of cellulosic textile material the improvement which comprises employing as the vat dyestuff a vat dyestuff according to claim 1 containing an acylamino group of the formula 17. In a process for the vat dyeing of cellulosic textile material the improvement which comprises employing as the vat dyestulf a vat dyestufi according to claim 1 containing an acylamino group of the formula 18. In a process for the vat dyeing of cellulosic textile material the improvement which comprises employing as the vat dyestuff a vat dyestufi according to claim 1 containing an acylamino group of the formula 19. In a process for the vat dyeing of cellulosic textile material the improvement which comprises employing as the vat dyestuff the vat dyestuff of the formula 20. In a process for the vat dyeing of cellulosic textile mate-rial the improvement which comprises employing as the vat dyestufi the vat dyestufi of the formula 21. In a process for the vat dyeing of cellulosic textile material the improvement which comprises employing as the vat dyestuif the vat dyestuff of the formula 22. In a process for the vat dyeing of cellulosic textile material the improvement which comprises employing as the vat dyest-ufl the vat dyestulf of the formula /orr NH-O o-Or-Ooo-mr c 31 23. In a process for the vat dyeing of cellulosic textile material the improvement which comprises employing as the vat dyestuff the vat dyestuff of the formula References Cited UNITED STATES PATENTS 1,801,709 4/1931 Zerwerk 260 274 5 1,845,469 2/1932 WOlif Ct al. 260-274 2,195,462 4/1940 Krause et al. 260-377 x 2,326,047 8/1943 McNally 61 a1. 260-379 0 2,464,831 3/1949 Stilmar 260-307.5 9 2,511,019 6/1950 Stilmar 260-307.5 2,567,821 9/1951 Moergeri 260--377 0 OH 10 2,629,718 2/1953 Belshaw et al. 260--307.5 R 2,670,265 2/1954 Heyna et a1. 8--49 N 2,723,279 11/1955 Hoeflfi 260-377 2,768,172 10/1956 Schmidt-Nickels 260-315 15 2,983,731 5/1961 Meis et a1. 260-315 3,134,731 5/1964 Wunderlich et al. 260-274 FOREIGN PATENTS 570,326 9/1961 Belgium. i, 20 NORMAN G. TORCHIN, Primary Examiner.

J. HERBERT, D. G. DAUS, Assistant Examiner. 

1. IN A PROCESS FOR THE VAT DYEING OF CELLULOSIC TEXTILE MATERIAL THE IMPROVEMENT WHICH COMPRISES, EMPLOYING AS THE VAT DYESTUFF A VAT DYESTUFF CONTAINING TWO MEMBERS OF THE GROUP CONSISTING OF THE ANTHRONE, ACRIDONE AND ANTHRAQUINONE GROUPING WHICH MAY BE CONDENSED TO A RING SYSTEM, AND ACYLAMINO GROUP CONTAINING A PHOSPHORIC ACID GROUPING BOUND TO ITS ACYL RADICAL AT LEAST TWO VATTABLE SYSTEMS AND AT LEAST ONE VAT-STABLE PHOSPHORIC ACID GROUPING. 